CN111180313A - Low-dislocation in-situ etching MOCVD secondary epitaxial growth method - Google Patents
Low-dislocation in-situ etching MOCVD secondary epitaxial growth method Download PDFInfo
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Abstract
A low dislocation in-situ etching MOCVD secondary epitaxial growth method comprises the following steps: carrying out in-situ etching treatment on the primary epitaxial wafer before the secondary epitaxy; and performing secondary epitaxial growth of InGaAsP, InAlGaAs, AlGaAs or AlGaInP materials on the primary epitaxial wafer after in-situ etching. HCl gas is introduced into a reaction chamber to be used as main etching gas, and PBr is introduced simultaneously3Or AsCl3The gas is used As a smoothing agent which is respectively used for supplementing and protecting a P-containing material or an As-containing material, so that in-situ etching of a primary epitaxial wafer is realized, defects and dislocation of the substrate surface appearance before MOCVD secondary epitaxial growth are reduced, and the secondary epitaxial growth quality is improved.
Description
Technical Field
The invention belongs to the field of optical communication and high-power semiconductor lasers, and particularly relates to an epitaxial growth method of an optical communication and high-power semiconductor laser chip.
Background
In recent years, high power semiconductor lasers have been playing a critical role in the present society because of their rapid development of laser technology. The high-power semiconductor laser has the advantages of small volume, light weight, high reliability, low power consumption, high efficiency, long service life and the like, is widely applied to various fields such as military affairs, industry, communication, medicine, scientific research and the like, and is a laser light source with the most development prospect in the future. In military affairs, the high-power pulse semiconductor laser is widely applied to laser guidance and laser ranging; in addition, the semiconductor laser is widely applied to the fields of laser radar, laser communication, laser gyro, laser aiming warning and the like, or is applied to a laser high-energy weapon pumping source and is used for direct military striking after closing. In industry, a high-power semiconductor laser is a main pumping source of an ytterbium-doped fiber laser, and the high-power semiconductor laser can output peak power as high as 20000W and is widely applied to the fields of laser marking, laser welding, laser cutting, laser cleaning and the like. The high-power pulse semiconductor laser can be used as a light source of laser radar, laser ranging and security equipment. The red, green and blue laser has the advantages of wide color gamut, long service life, high brightness, easy large-screen display, energy conservation, environmental protection and the like, and becomes an excellent light source of the laser television. In medicine, the high-power semiconductor laser can be used in the fields of myopia treatment, freckle removing and beauty treatment, hair removal, surgical minimally invasive surgery and the like, and plays an important role in aspects of soft tissue excision, coagulation and gasification, tissue joining and the like. In scientific research, the laser is widely applied to multiple subject fields by the characteristics of the laser, such as the fastest knife, the brightest light, the most accurate ruler and the like.
In order to meet different requirements, lasers have also developed different structures. Distributed Feedback Laser (DFB) semiconductor lasers have excellent properties such as Tunable wavelength, narrow linewidth, and high-speed modulation, and have been widely used in the fields of communication, absorption spectrum detection Technology (TDLAS), Laser radar, pump light source, optical integration, etc., there is a grating structure in the DFB semiconductor Laser epitaxial wafer, and the manufacturing of the grating needs to etch the epitaxial wafer and then perform secondary epitaxy. The buried heterostructure laser has a series of advantages of stable waveguide mode, low threshold current, quasi-symmetrical light beam distribution and the like, and the manufacture of the buried heterostructure laser needs to etch a primary epitaxial wafer and then carry out secondary epitaxy. InP and its series compound semiconductor materials are developed mainly in response to the requirement of long-wavelength optical communication, quartz fiber has two windows of low dispersion at 1.3 μm wavelength and low loss at 1.55 μm wavelength, and InP and its matched InGaAsP compound band edge wavelength is 0.92-1.65 μm, just covering these two windows, which is an important material in optical communication. Basal plane dislocations appear in the epitaxial growth process, and the generation of the basal plane dislocations has great relation with the surface appearance and defects of the substrate before epitaxial growth, so that the surface defects and the dislocations are eliminated before the growth to the greatest extent, and the subsequent film growth quality is greatly influenced.
Disclosure of Invention
Technical problem to be solved
The invention mainly aims to provide a low-dislocation in-situ etching MOCVD secondary epitaxial growth method, so as to reduce the problems of defects and dislocations in the substrate surface appearance before MOCVD secondary epitaxial growth.
(II) technical scheme
The invention provides a low dislocation in-situ etching MOCVD secondary epitaxial growth method, which comprises the following steps:
carrying out in-situ etching treatment on the primary epitaxial wafer before the secondary epitaxy; and
and performing secondary epitaxial growth of InGaAsP, InAlGaAs, AlGaAs or AlGaInP materials on the primary epitaxial wafer after in-situ etching.
In the above scheme, the in-situ etching process of the primary epitaxial wafer before the secondary epitaxy comprises:
introducing HCl gas as main etching gas into the reaction chamber, and introducing PBr3Or AsCl3And the gas is used As a smoothing agent which is respectively used for supplementing and protecting a P-containing material or an As-containing material, so that the in-situ etching of the primary epitaxial wafer is realized.
Wherein, PBr as smoothing agent3Or AsCl3The gas is H by bubbling2Gas-borne PBr3Or AsCl3Gas entryA reaction chamber.
In the step of carrying out in-situ etching treatment on the primary epitaxial wafer before secondary epitaxy, introducing PH into the reaction chamber3Or AsH3And (5) protecting the gas.
In the above scheme, the secondary epitaxial growth of the InGaAsP, InAlGaAs, AlGaAs or AlGaInP material is performed on the primary epitaxial wafer after in-situ etching, and the secondary epitaxial growth includes:
MOCVD equipment adopts TMGa, TMIn and TMAl as III group source, PH3And AsH3As a V-group source, performing secondary epitaxial growth of InGaAsP material on the primary epitaxial wafer after in-situ etching; or
MOCVD equipment adopts TMGa, TMIn and TMAl as III group source, AsH3As a V-group source, carrying out InAlGaAs material secondary epitaxial growth on the primary epitaxial wafer after in-situ etching; or
MOCVD equipment adopts TMGa and TMAl as III family source, AsH3As a V-family source, carrying out secondary epitaxial growth of AlGaAs material on the primary epitaxial wafer after in-situ etching; or
MOCVD equipment adopts TMGa, TMAl and TMIn as III group source, PH3And as a V-group source, carrying out secondary epitaxial growth of AlGaInP material on the primary epitaxial wafer after in-situ etching.
And performing secondary epitaxial growth of the InGaAsP material on the primary epitaxial wafer after in-situ etching, wherein the thickness of the grown InGaAsP material is 0.5-3.5 mu m, the growth temperature is 580-680 ℃, the pressure of a reaction chamber is 50-150 mbar, and the source ratio of V to III is 100-260.
Wherein, MOCVD equipment adopts TMGa, TMIn and TMAl as III group source, AsH3And (3) taking the InAlGaAs material as a group V source, carrying out secondary epitaxial growth on the InAlGaAs material on the primary epitaxial wafer after in-situ etching, wherein the growth temperature is 580-680 ℃, the pressure of the reaction chamber is 50-150 mbar, and the group V-III source ratio is 100-260.
And performing secondary epitaxial growth of AlGaAs material on the primary epitaxial wafer after in-situ etching at the growth temperature of 650-750 ℃, the source ratio of V to III is 60-100 and the growth pressure is 5000-10000 Pa.
And performing secondary epitaxial growth of AlGaInP material on the primary epitaxial wafer after in-situ etching at the growth temperature of 650-750 ℃, the source ratio of V to III is 60-100 and the growth pressure is 5000-10000 Pa.
(III) advantageous effects
The low dislocation in-situ etching MOCVD secondary epitaxial growth method provided by the invention introduces HCl gas as main etching gas into a reaction chamber and simultaneously introduces PBr3Or AsCl3The gas is used As a smoothing agent which is respectively used for supplementing and protecting a P-containing material or an As-containing material, so that in-situ etching of a primary epitaxial wafer is realized, defects and dislocation of the substrate surface appearance before MOCVD secondary epitaxial growth are reduced, and the secondary epitaxial growth quality is improved.
Drawings
Fig. 1 is a flow chart of a low dislocation in-situ etching MOCVD secondary epitaxial growth method according to an embodiment of the invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to specific embodiments and the accompanying drawings.
As shown in fig. 1, fig. 1 is a flowchart of a low dislocation in-situ etching MOCVD secondary epitaxial growth method according to an embodiment of the invention, and the method includes:
carrying out in-situ etching treatment on the primary epitaxial wafer before the secondary epitaxy;
and performing secondary epitaxial growth of InGaAsP, InAlGaAs, AlGaAs or AlGaInP materials on the primary epitaxial wafer after in-situ etching.
Specifically, the in-situ etching treatment of the primary epitaxial wafer before the secondary epitaxy comprises the following steps:
growing a primary epitaxial wafer on the surface of a substrate;
step two, growing SiO on the primary epitaxial wafer2Carrying out photoetching and etching on the film;
and step three, carrying out in-situ etching on the primary epitaxial wafer.
In order to explain the growing process of InGaAsP, InAlGaAs, AlGaAs or AlGaInP material on the primary epitaxial wafer after in-situ etching in detail, the invention provides four embodiments, which respectively explain the growing process of the four materials in detail.
Example one
The first embodiment is used to illustrate the process of performing the secondary epitaxial growth of InGaAsP material on the primary epitaxial wafer after in-situ etching.
Specifically, the process of performing in-situ etching treatment on the primary epitaxial wafer before the secondary epitaxy comprises the steps of one to three.
Step one, growing a primary epitaxial wafer containing the InGaAsP material on the surface of the substrate.
MOCVD uses TMGa, TMIn as group III source, PH3And AsH3Used as a group V source. The TMGa source temperature is chosen to be 0 ℃, which is relatively low and easy to control. TMIn is a solid source, the source temperature is selected to be 17 ℃, and the TMIn is ensured to have stable saturated vapor pressure. TMIn source flow of 10 mu mol/min, carrying gas flow of 50ml/min, and selected PH3And AsH3The concentrations were all 100%. The growth temperature is 580 to 680 ℃. An epitaxial wafer of 0.5 to 2.5 μm thickness is grown on the substrate.
Step two, growing SiO on the primary epitaxial wafer2And photoetching and etching the film.
Growing a layer of SiO on a primary epitaxial wafer by PECVD2And (5) making a mask. The reaction gas is SiH4And N2O, flowing through the Deposition zone in a mid-stream manner, Plasma Enhanced Chemical Vapor Deposition (PECVD) of silicon dioxide is carried out by surface adsorption and the heterogeneous radical principle, SiH, increased by low-energy ion bombardment4And N2O generates glow discharge through a radio frequency electric field under certain low pressure, gas molecules are activated, molecular bonds are opened, plasma which is composed of high-energy active ions and has quite complex components is formed, and the reaction equation is as follows
SiH4+N2O＝SiO2+2H2O+N2
The reaction temperature is 150 ℃ to 300 ℃, SiH4The flow rate is 0.5 to 1L/min, N2O flow rate of 1 to 1.5L/min, and precipitation pressureForce 0.8-2Torr, degree of vacuum of 2X 10-2Torr, precipitation rate 150 to
And coating a layer of photoresist with certain thickness, uniform thickness and no dust and impurity on the surface of the primary epitaxial wafer. And (3) dripping photoresist on the surface of the primary epitaxial wafer, and homogenizing the photoresist by using a homogenizer, wherein the rotation speed is 700rpm and the rotation time is 7s, and the rotation speed is 3000rpm and the rotation time is 40 s. And pre-baking the primary epitaxial wafer, putting the wafer coated with the photoresist into a pre-baking machine at the temperature of 110 ℃ for baking for 2 minutes to promote the solvent in the photoresist film to be fully volatilized, drying the photoresist film, and increasing the strength of the photoresist film to ensure that the photoresist film is firmly adhered to the sample wafer. And (3) putting the primary epitaxial wafer into a photoetching machine, and sequentially carrying out the steps of plate sucking, wafer sucking, lifting-contacting, adhering, exposing and the like on the photoetching machine. AZ 300MIF developer was used and rinsed with deionized water for about 40 seconds and then rinsed for 2 minutes. Hardening is carried out in an oven, the hardening temperature is 120 ℃, and the hardening time is about 120 s.
The etching adopts a coupled induction plasma (ICP) dry etching technology, adopts hydrocarbon-based gas, namely CH, by optimizing the gas ratio4、H2And performing dry etching on the mixed gas of Ar and the mixed gas of Ar, wherein the etching materials are different, the etching gas is the same, and the same gas has different physical and chemical actions on different materials, so that the etching speed is different. And after the dry etching is finished, removing the residual silicon dioxide on the surface by using a hydrofluoric acid solution, and corroding the primary epitaxial wafer for 20s by using a mixed solution of concentrated sulfuric acid, hydrogen peroxide and water.
And step three, carrying out in-situ etching on the primary epitaxial wafer.
Introducing pure HCl gas as main etching gas into the reaction chamber under low pressure, and allowing H2 to carry PBr as smoothing agent by a bubbler3Gas enters the reaction chamber and PH is introduced3And supplementing and protecting the P material. The etching rate is controlled to be 1 to 20nm/s, and the etching pressure is controlled to be 5 to 20 mbar. Introduction into PBr3The flow rate is 100ml/min, the time is 30s, and the etching depth is 50 nm. By adjustingThe whole is introduced with HCl and BrP3The etching speed and depth can be controlled by the concentration and time of the etching solution, and the etching degree can be adjusted according to the process requirement.
The principle of in-situ etching is as follows:
HCl(g)+InP(s)＝InCl3(g)+PH3(g)
and performing secondary epitaxial growth of the InGaAs material on the primary epitaxial wafer after in-situ etching.
And fourthly, performing secondary epitaxial growth of the InGaAsP material on the primary epitaxial wafer after in-situ etching.
MOCVD equipment adopts TMGa, TMIn and TMAl as III group source, PH3And AsH3And taking the InGaAsP material as a V-group source, and carrying out secondary epitaxial growth on the InGaAsP material on the primary epitaxial wafer after in-situ etching, wherein the growth thickness is 0.5-3.5 mu m. The TMIn source flow of the chip and the carrier gas flow were 50 ml/min. Selecting pH3And AsH3The concentrations were all 100%. The growth temperature is 580 to 680 ℃, the pressure in the reaction chamber is 50 to 150mbar, the ratio of the V to the III source is 100 to 260, and the growth rate is 18 to 72 nm/min. And completing the in-situ etching, namely the secondary epitaxial growth process.
Example two
The embodiment is used for explaining the secondary epitaxial growth process of InAlGaAs material on the primary epitaxial wafer after in-situ etching.
The flow chart of the MOCVD secondary epitaxial growth method of the low dislocation in-situ etching according to the embodiment of the invention comprises the following steps:
carrying out in-situ etching treatment on the primary epitaxial wafer before the secondary epitaxy;
and carrying out secondary epitaxial growth of InAlGaAs material on the primary epitaxial wafer after in-situ etching.
Specifically, the process of performing in-situ etching treatment on the primary epitaxial wafer before the secondary epitaxy comprises the steps of one to three.
Step one, growing a primary epitaxial wafer containing InAlGaAs material on the surface of a substrate. MOCVD uses TMGa, TMIn, TMAl as III group source, AsH3Used as a group V source. The TMGa source temperature is selected to be-0 ℃, which is low and easy to control. TMIn is solid source, and its source temperature is selectedThe temperature is 17 ℃, and TMIn is ensured to have stable saturated vapor pressure. TMIn source flow of 10 mu mol/min, carrying gas flow of 50ml/min, and selected PH3And AsH3The concentrations were all 100%. The growth temperature is 580 to 680 ℃. A 0.5 to 3.5 μm thick primary epitaxial wafer is grown on the substrate.
Step two, growing SiO on the primary epitaxial wafer2And photoetching and etching the film.
Growing a layer of SiO on a primary epitaxial wafer by PECVD2And (5) making a mask. The reaction gas is SiH4And N2O, flowing through the Deposition zone in a mid-stream manner, Plasma Enhanced Chemical Vapor Deposition (PECVD) of silicon dioxide is carried out by surface adsorption and the heterogeneous radical principle, SiH, increased by low-energy ion bombardment4And N2O generates glow discharge through a radio frequency electric field under certain low pressure, gas molecules are activated, molecular bonds are opened, plasma which is composed of high-energy active ions and has quite complex components is formed, and the reaction equation is as follows
SiH4+N2O＝SiO2+2H2O+N2
The reaction temperature is 150 ℃ to 300 ℃, SiH4The flow rate is 0.5 to 1L/min, N2O flow of 1 to 1.5L/min, precipitation pressure of 0.8 to 2Torr, degree of vacuum of 2X 10 to 2Torr, precipitation rate of 150 to
And coating a layer of photoresist with a certain thickness, uniform thickness and no dust and impurity on the surface of the primary epitaxial wafer. And (3) dripping photoresist on the surface of the primary epitaxial wafer, and homogenizing the photoresist by using a homogenizer, wherein the rotation speed is 700rpm and the rotation time is 7s, and the rotation speed is 3000rpm and the rotation time is 40 s. And pre-baking the primary epitaxial wafer, putting the wafer coated with the photoresist into a pre-baking machine at the temperature of 110 ℃ for baking for 2 minutes to promote the solvent in the photoresist film to be fully volatilized, drying the photoresist film, and increasing the strength of the photoresist film to ensure that the photoresist film is firmly adhered to the sample wafer. And (3) putting the primary epitaxial wafer into a photoetching machine, and sequentially carrying out the steps of plate sucking, wafer sucking, lifting-contacting, adhering, exposing and the like on the photoetching machine. AZ 300MIF developer was used and rinsed with deionized water for about 40 seconds and then rinsed for 2 minutes. Hardening is carried out in an oven, the hardening temperature is 120 ℃, and the hardening time is about 120 s.
The etching adopts a coupled induction plasma (ICP) dry etching technology, adopts hydrocarbon-based gas, namely CH, by optimizing the gas ratio4、H2And performing dry etching on the mixed gas of Ar and the mixed gas of Ar, wherein the etching materials are different, the etching gas is the same, and the same gas has different physical and chemical actions on different materials, so that the etching speed is different. And after the dry etching is finished, removing the residual silicon dioxide on the surface by using a hydrofluoric acid solution, and corroding the primary epitaxial wafer for 20s by using a mixed solution of concentrated sulfuric acid, hydrogen peroxide and water.
And step three, carrying out in-situ etching on the primary epitaxial wafer.
Introducing pure HCl gas as main etching gas into the reaction chamber under low pressure, and bubbling H gas through a bubbler2Carrying PBr as smoothing agent3Gas enters the reaction chamber and PH is introduced3And (6) protecting. The etching rate is controlled to be 1 to 20nm/s, and the etching pressure is controlled to be 5 to 20 mbar. Introduction into PBr3The flow rate is 100ml/min, the time is 30s, and the etching depth is 50 nm. By adjusting the passage of HCl and BrP3The etching speed and depth can be controlled by the concentration and time of the etching solution, and the etching degree can be adjusted according to the process requirement.
The principle of in-situ etching is as follows:
HCl(g)+InP(s)＝InCl3(g)+PH3(g)
and performing a secondary epitaxial growth process of the InAlGaAs material on the primary epitaxial wafer after the in-situ etching comprises a fourth step.
And fourthly, carrying out secondary epitaxial growth of InAlGaAs material on the primary epitaxial wafer after in-situ etching.
MOCVD equipment adopts MOCVD and adopts TMGa, TMIn and TMAl as group III source, AsH3Used as a group V source. And carrying out secondary epitaxial growth of InAlGaAs material on the primary epitaxial wafer after in-situ etching. TMIn source flow rate of 5-10 mu mol/min and carrying gas flow rate of 50ml/min. Selecting pH3And AsH3The concentrations were all 100%. The growth temperature is 580 to 680 ℃, the pressure in the reaction chamber is 50 to 150mbar, the V/III ratio is 100 to 260, and the growth rate is 18 to 72 nm/min. And completing the in-situ etching, namely the secondary epitaxial growth process.
EXAMPLE III
The example serves to illustrate the process of secondary epitaxial growth of AlGaAs material on the primary epitaxial wafer after in-situ etching. The invention provides a low dislocation in-situ etching MOCVD secondary epitaxial growth method, which comprises the following steps:
carrying out in-situ etching treatment on the primary epitaxial wafer before the secondary epitaxy;
and carrying out secondary epitaxial growth of AlGaAs material on the primary epitaxial wafer after in-situ etching.
Specifically, the process of performing in-situ etching treatment on the primary epitaxial wafer before the secondary epitaxy comprises the steps of one to three.
Step one, growing a primary epitaxial wafer containing AlGaAs material on the surface of the substrate.
Substrate sheet adopts
The crystal orientation of the N-type GaAs substrate material is deviated from (100) to (111) by 4-15 degrees, and the commercial cleaning-free substrate material is used. The three-family source used for growing AlGaAs material by MOCVD equipment is TMGa and TMAl, and the five-family source is AsH3，AsH3The concentration was 100%. N type material dopant is 2% SiH4The P-type AlGaAs dopant is DEZn or CCl4、CBr4. The growth temperature is 650 to 750 ℃, the V/III ratio is 60 to 100, and the growth pressure is 5000 to 10000 Pa. A 0.5 to 3.5 μm thick primary epitaxial wafer is grown on a GaAs substrate.
Step two, growing SiO on the primary epitaxial wafer2And photoetching and etching the film.
Growing a layer of SiO on a primary epitaxial wafer by PECVD2And (5) making a mask. The reaction gas is SiH4And N2O, flowing through the deposition zone in an intermediate manner, plasma enhanced chemical vapor deposition of silicon dioxide by surface adsorption and heterogeneous radical mechanism enhanced by low energy ion bombardmentOf row, SiH4And N2The gas molecules are activated and the molecular bonds are opened to form plasma which is composed of high-energy active ions and has quite complex components, and the reaction equation is as follows:
SiH4+N2O＝SiO2+2H2O+N2
the reaction temperature is 150 ℃ to 300 ℃, SiH4The flow rate is 0.5 to 1L/min, N2O flow of 1 to 1.5L/min, precipitation pressure of 0.8 to 2Torr, degree of vacuum of 2X 10 to 2Torr, precipitation rate of 150 to
And coating a layer of photoresist with a certain thickness, uniform thickness and no dust and impurity on the surface of the primary epitaxial wafer. And (3) dripping photoresist on the surface of the epitaxial wafer, and homogenizing the photoresist by using a homogenizer, wherein the rotation speed is 700rpm and the rotation time is 7s, and the rotation speed is 3000rpm and the rotation time is 40 s. And pre-baking the primary epitaxial wafer, putting the wafer coated with the photoresist into a pre-baking machine at the temperature of 110 ℃ for baking for 2 minutes to promote the solvent in the photoresist film to be fully volatilized, drying the photoresist film, and increasing the strength of the photoresist film to ensure that the photoresist film is firmly adhered to the sample wafer. And (3) putting the primary epitaxial wafer into a photoetching machine, and sequentially carrying out the steps of plate sucking, wafer sucking, lifting-contacting, adhering, exposing and the like on the photoetching machine. AZ 300MIF developer was used and rinsed with deionized water for about 40 seconds and then rinsed for 2 minutes. Hardening is carried out in an oven, the hardening temperature is 120 ℃, and the hardening time is about 120 s.
The etching adopts a coupled induction plasma (ICP) dry etching technology, adopts hydrocarbon-based gas, namely CH, by optimizing the gas ratio4/H2The dry etching is carried out by the mixed gas of/Ar, the etching materials are different, the gas used for etching is the same, and the same gas has different physical and chemical actions on different materials, so that the etching speed is different. And after the dry etching is finished, removing the residual silicon dioxide on the surface by using a hydrofluoric acid solution, and corroding the primary epitaxial wafer for 20s by using a mixed solution of concentrated sulfuric acid, hydrogen peroxide and water.
And step three, carrying out in-situ etching on the primary epitaxial wafer.
Introducing pure HCl gas as main etching gas into the reaction chamber under low pressure, and bubbling H gas through a bubbler2Carrying AsCl as smoothing agent3Gas enters the reaction chamber and is introduced into the AsH3And supplementing and protecting As materials. The etching rate is controlled to be 1 to 20nm/s, and the etching pressure is controlled to be 5 to 20 mbar. Introduction of AsH3The flow rate is 100ml/min, the time is 30s, and the etching depth is 50 nm. By adjusting the introduction of HCl and AsCl3The etching speed and depth can be controlled by the concentration and time of the etching solution, and the etching degree can be adjusted according to the process requirement.
The principle of in-situ etching is as follows:
3HCl(g)+GaAs(s)＝GaCl3(g)+AsH3(g)
and performing secondary epitaxial growth of the AlGaAs material on the primary epitaxial wafer after in-situ etching.
And fourthly, carrying out secondary epitaxial growth of the AlGaAs material on the primary epitaxial wafer after in-situ etching.
The three-family source used for growing AlGaAs material by MOCVD equipment is TMGa and TMAl, and the five-family source is AsH3，AsH3The concentration was 100%. N type material dopant is 2% SiH4The P-type AlGaAs dopant is DEZn or CCl4、CBr4. The growth temperature is 650 to 750 ℃, the V/III ratio is 60 to 100, and the growth pressure is 5000 to 10000 Pa.
Example four
Example four is used to illustrate the secondary epitaxial growth of AlGaInP material on the primary epitaxial wafer after in-situ etching.
The invention provides a low-dislocation in-situ etching MOCVD secondary epitaxial growth method, which comprises the following steps:
carrying out in-situ etching treatment on the primary epitaxial wafer before the secondary epitaxy;
and carrying out secondary epitaxial growth of AlGaInP material on the primary epitaxial wafer after in-situ etching.
Specifically, the process of performing in-situ etching treatment on the primary epitaxial wafer before the secondary epitaxy comprises the steps of one to three.
Step one, growing a primary epitaxial wafer containing AlGaInP material on the surface of the substrate.
Substrate sheet adopts
The crystal orientation of the N-type GaAs substrate material is deviated from (100) to (111) by 4-15 degrees, and the commercial cleaning-free substrate material is used. The three-family source used for growing AlGaAs material by MOCVD equipment is TMGa and TMAl, and the five-family source is AsH3，AsH3The concentration was 100%. N type material dopant is 2% SiH4The P-type AlGaAs dopant is DEZn or CCl4、CBr4. The growth temperature is 650 to 750 ℃, the V/III ratio is 60 to 100, and the growth pressure is 5000 to 10000 Pa. AlGaInP primary epitaxial wafers 0.5 to 3.5 μm thick are grown on GaAs substrates.
Step two, growing SiO on the primary epitaxial wafer2And photoetching and etching the film.
Growing a layer of SiO on a primary epitaxial wafer by PECVD2And (5) making a mask. The reaction gas is SiH4And N2O, flowing through the deposition zone in an in-between manner, Plasma Enhanced Chemical Vapor Deposition (PECVD) of silicon dioxide by surface adsorption and heterogeneous radical principles augmented by low energy ion bombardment, SiH4And N2O generates glow discharge through a radio frequency electric field under certain low pressure, gas molecules are activated, molecular bonds are opened, plasma which is composed of high-energy active ions and has quite complex components is formed, and the reaction equation is as follows
SiH4+N2O＝SiO2+2H2O+N2
The reaction temperature is 150 ℃ to 300 ℃, SiH4The flow rate is 0.5 to 1L/min, N2O flow of 1 to 1.5L/min, precipitation pressure of 0.8 to 2Torr, degree of vacuum of 2X 10 to 2Torr, precipitation rate of 150 to
And coating a layer of photoresist with a certain thickness, uniform thickness and no dust and impurity on the surface of the primary epitaxial wafer. And (3) dripping photoresist on the surface of the primary epitaxial wafer, and homogenizing the photoresist by using a homogenizer, wherein the rotation speed is 700rpm and the rotation time is 7s, and the rotation speed is 3000rpm and the rotation time is 40 s. And pre-baking the primary epitaxial wafer, putting the wafer coated with the photoresist into a pre-baking machine at the temperature of 110 ℃ for baking for 2 minutes to promote the solvent in the photoresist film to be fully volatilized, drying the photoresist film, and increasing the strength of the photoresist film to ensure that the photoresist film is firmly adhered to the sample wafer. And (4) putting the primary epitaxial wafer into a photoetching machine, and sequentially carrying out plate suction, wafer suction and rinsing on the photoetching machine, wherein after the developing time is about 40s, rinsing is carried out for 2 minutes. Hardening is carried out in an oven, the hardening temperature is 120 ℃, and the hardening time is about 120 s.
The etching adopts a coupled induction plasma (ICP) dry etching technology, adopts hydrocarbon-based gas, namely CH, by optimizing the gas ratio4/H2The dry etching is carried out by the mixed gas of/Ar, the etching materials are different, the gas used for etching is the same, and the same gas has different physical and chemical actions on different materials, so that the etching speed is different. And after the dry etching is finished, removing the residual silicon dioxide on the surface by using a hydrofluoric acid solution, and corroding the primary epitaxial wafer for 20s by using a mixed solution of concentrated sulfuric acid, hydrogen peroxide and water.
And step three, carrying out in-situ etching on the primary epitaxial wafer.
Introducing pure HCl gas as main etching gas into the reaction chamber under the low pressure state, and enabling H2 to carry AsCl as a smoothing agent through a bubbler3Gas enters the reaction chamber and is introduced into the AsH3And (6) protecting. The etching rate is controlled to be 1 to 20nm/s, and the etching pressure is controlled to be 5 to 20 mbar. Introduction of AsH3The flow rate is 100ml/min, the time is 30s, and the etching depth is 50 nm. By adjusting the introduction of HCl and AsCl3The etching speed and depth can be controlled by the concentration and time of the etching solution, and the etching degree can be adjusted according to the process requirement.
The principle of in-situ etching is as follows:
3HCl(g)+GaAs(s)＝GaCl3(g)+AsH3(g)
and performing secondary epitaxial growth of the AlGaInP material on the primary epitaxial wafer after in-situ etching.
And fourthly, carrying out secondary epitaxial growth of the AlGaInP material on the primary epitaxial wafer after in-situ etching.
The three-group source used for growing AlGaInP material by MOCVD equipment is TMGa, TMAI and TMIn, and the five-group source is PH3，AsH3The concentration was 100%. N type material dopant is 2% SiH4The P-type AlGaAs dopant is DEZn or CCl4、CBr4. TMIn is a solid source, the source temperature is selected to be 17 ℃, and the TMIn is ensured to have stable saturated vapor pressure. TMIn source flow of 10 mu mol/min, carrying gas flow of 50ml/min, growth temperature of 650-750 ℃, V/III ratio of 60-100, growth pressure of 5000-10000 Pa.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are only exemplary embodiments of the present invention, and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (9)
1. A low dislocation in-situ etching MOCVD secondary epitaxial growth method is characterized by comprising the following steps:
carrying out in-situ etching treatment on the primary epitaxial wafer before the secondary epitaxy; and
and performing secondary epitaxial growth of InGaAsP, InAlGaAs, AlGaAs or AlGaInP materials on the primary epitaxial wafer after in-situ etching.
2. The low dislocation in-situ etching MOCVD secondary epitaxial growth method of claim 1, wherein the in-situ etching treatment of the primary epitaxial wafer before the secondary epitaxy comprises:
introducing HCl gas as main etching gas into the reaction chamber, and introducing PBr3Or AsCl3And the gas is used As a smoothing agent which is respectively used for supplementing and protecting a P-containing material or an As-containing material, so that the in-situ etching of the primary epitaxial wafer is realized.
3. The low dislocation in-situ etching MOCVD secondary epitaxial growth method of claim 2, wherein the PBr as smoothing agent3Or AsCl3The gas is H by bubbling2Gas-borne PBr3Or AsCl3The gas enters the reaction chamber.
4. The MOCVD secondary epitaxial growth method with low dislocation in-situ etching according to claim 2 or 3, wherein in the step of performing in-situ etching treatment on the primary epitaxial wafer before secondary epitaxy, PH is introduced into the reaction chamber3Or AsH3And (5) protecting the gas.
5. The MOCVD secondary epitaxial growth method according to claim 1, wherein the secondary epitaxial growth of InGaAsP, InAlGaAs, AlGaAs or AlGaInP material is performed on the primary epitaxial wafer after in-situ etching, and the method comprises the following steps:
MOCVD equipment adopts TMGa, TMIn and TMAl as III group source, PH3And AsH3As a V-group source, performing secondary epitaxial growth of InGaAsP material on the primary epitaxial wafer after in-situ etching; or
MOCVD equipment adopts TMGa, TMIn and TMAl as III group source, AsH3As a V-group source, carrying out InAlGaAs material secondary epitaxial growth on the primary epitaxial wafer after in-situ etching; or
MOCVD equipment adopts TMGa and TMAl as III family source, AsH3As a V-family source, carrying out secondary epitaxial growth of AlGaAs material on the primary epitaxial wafer after in-situ etching; or
MOCVD equipment adopts TMGa, TMAl and TMIn as III group source, PH3And as a V-group source, carrying out secondary epitaxial growth of AlGaInP material on the primary epitaxial wafer after in-situ etching.
6. The MOCVD secondary epitaxial growth method with low dislocation in situ etching according to claim 5, wherein the secondary epitaxial growth of InGaAsP material is performed on the primary epitaxial wafer after in situ etching, the thickness of the grown InGaAsP material is 0.5-3.5 μm, the growth temperature is 580-680 ℃, the pressure of the reaction chamber is 50-150 mbar, and the source ratio of V to III is 100-260.
7. The MOCVD secondary epitaxial growth method for low dislocation in-situ etching according to claim 5, wherein the MOCVD equipment adopts TMGa, TMIn and TMAl as III group source, AsH3And (3) taking the InAlGaAs material as a group V source, carrying out secondary epitaxial growth on the InAlGaAs material on the primary epitaxial wafer after in-situ etching, wherein the growth temperature is 580-680 ℃, the pressure of the reaction chamber is 50-150 mbar, and the group V-III source ratio is 100-260.
8. The MOCVD secondary epitaxial growth method of low dislocation in-situ etching according to claim 5, wherein the secondary epitaxial growth of AlGaAs material is carried out on the primary epitaxial wafer after in-situ etching, the growth temperature is 650 to 750 ℃, the ratio of V to III source is 60 to 100, and the growth pressure is 5000 to 10000 Pa.
9. The MOCVD secondary epitaxial growth method for low dislocation in-situ etching according to claim 5, wherein the secondary epitaxial growth of AlGaInP material is carried out on the primary epitaxial wafer after in-situ etching, the growth temperature is 650 to 750 ℃, the ratio of V to III source is 60 to 100, and the growth pressure is 5000 to 10000 Pa.
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| CN117438284A (en) * | 2022-07-12 | 2024-01-23 | 江苏第三代半导体研究院有限公司 | Etching method, secondary epitaxy method and application of semiconductor epitaxy structure |
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